Batch distillation



mg @9 T. A1-Kms, JR 294059393 BATCH DISTILLATION Filed Dec. 25, 1941 4 swam-snee@ 1 ugf; B946. T. ATKlNs, JR 2,@@593 BATCH DISTILLATION Filed nec. 25,1941 A. sheefs-sheet 2 FEACT/ONAT/NG Co/ uM/V v I y 2/ /8 20 I 1-L g 22 S TILL Ffa-2 G. vT. ATKINS, JR

BATCH DISTILLATION Filed Dec. 23, 1941 4 Sheets-Sheet 4 Patented Aug. 6, 1946 BATCH DISTILLATION George T. Atkins, Jr., Highlands, Tex., assigner to Standard Oil Development Company, a corporation of Delaware Application December 23, 1941, Serial No. 424,165

3 Claims.

The present invention relates to an improvedV method of distilling liquids containing a plurality of components. tion of my present invention relates to the batch A particularly valuable applicawithdrawn from the top through line 5, are condensed in cooling coil I0, and lare thence discharged through line I2 into a receiving drum I5. Vapors .which are not condensed in cooling distillation of petroleum oils under conditions e011 In under-,the conditions of operation may be such that the distillation may be carried out in vented from the system through line I6. Dui'- given equipment at a greater rate than has been ing .the initial stages of the distillation, the unit possible heretofore. is operated under total reflux, that is to say, all

One Object 'of my present invention is to carry of the material collected in receiving druml l5 is out the batch distillation of a liquid charging Withdrawn through line I8 and recycled by pump Stock CODaIliIlg a plurality 0f Components n 20 to a point in the fractionating column above such a manner as to secure desired components the top plate thereof. This phase of the-distilat a greater rate than has been heretofore poslation continues until the plateswithin the vtower sible. i v contain the normal quantity of liquid and until Another object of my present invention is t0 15 suicient liquid has been supplied by the distildistill, in a batch operation, a petroleum oil in a process wherein I am enabled to perform the distillation more economically and rapidly than has been heretofore possible.

My invention will be best understood by reference to the accompanying drawings in which I have shown in Figure 1 diagrammatically a form and arrangement of apparatus elements embodying a preferred modification of my invention.

In Figure 2 I have shown schematically a further modication of my invention.

In Figure 3 draw-off line 40 and column 3 are shown in partial section.

In Figure 4, I have shown diagrammatically a preferred embodiment of my invention in which a batch distillation is conducted in a series of finite steps.

Figure 5 is an enlarged detail showing of Aa hold-up drum forming an important feature of my invention. V

Similar reference characters apply to similar parts throughout the several views.

I shall now proceedto set yforth a specific example illustrating my invention by means of a full description of a distilling operation embodying said invention, and, in so doing, I sha/ll refer to the accompanying drawings, but it is to be distinctly understood that the precise details I am about to set forth are purely illustrative and do not constitute va limitation on my invention.

Referring in detail to Figure 1, a batch still I is charged with, say, 1,000 gallons of a crude petroleum oil. Inr the modification I have shown. a fractionating column 3 of the usual bubble cap plate tower construction is superimposed, as shown, upon the said still. The oil in the still maybe heated by any conventional method, such as by a flame or steam or by any other known method. As heat isv applied,l the oil begins to vaporize and vapors passing up saidtcolumn are lation to fill a hold-up drum 2l, which is in communication with Yfractionating column 3 on the inlet side through line 25, and on the outlet side through line 28 and pump 29.

In order to further improve the distillation and fractionation of the charging stock to remove desired products, I provide in the lower part of the fractionating column 3, weirs and pipes to proportion and handle the liquid flowing in column 3 in the Vicinity of the inlet to line 25. It

is well known to divide a, liquidreflux stream into two portions inside a distillation column, to control the relative amounts of the two portions. to withdraw one portion as a draw-oilE stream from the column and to direct the other stream down-1 01T pipe is disposed with its upper end just below the normal liquid level on the plate and just above the point at which liquid is withdrawn from the tower through line 25. I also provide on the plate a second down pipe 4I (see Figure 3) and it will be noted that this pipe extends above the liquid level on the plate and carries a notch Il having a horizontal dimension approximately 20% ofthe weir length of the draw-off box 40, which supplies liquid to line 25. VThe above-mentioned horizontal dimension may vary normally from 10 to 30% of the weir length.

f During the lling of the hold-up drum 2l, the initial material withdrawn from the tower through line 25 constitutes the lightest fractions of the charging stock exceptgrwhere non-con,- densd vapors are vented through pipe It' (see Figure 1), since the tower is operating under conditions of total reflux. As the distillation proceeds, the fractions withdrawn through line progressively increase in boiling points. After drum 21 has been filled with liquid, valve 2| in line 22, which is in communication with line I3, is opened and the withdrawal of products is begun. At this point in the operation, the material returned to the tower in line 28 ,has approximately'the same boiling range as the product in the reflux line. The fraction returned to column 3 from hold-up drum 21 has a somewhat higher boiling point than the reflux; nevertheless, it serves as a satisfactory substitutefor at least a substantial part oftherefiux normally. employed in line I8. Thus, by returning liquid through line 28, less refluxv need be returned through line I8 and, consequently, the amount of product withdrawn through line I8, valve EI, and line 22 in a given unit of time, is greater than is normally obtainable when operating a batchdistillation unit of the same size in conventional manner.

After the removal of the initial material, the next successive fraction is then distilled and the operation continues progressively through fractions of higher and higher boiling point until the distillation has been completed and a iinal residue is produced in the still which is withdrawn through valve 1 and line 8 and is further processed, or alternatively, cooled and stored in equipment not shown. In the production of the distillate fractions of successively higher boiling point, reflux is supplied to the top of column 3 through line I8 in constant or varied amountaccording to the required purity of the component or fraction being distilled, higher, ratios of reux to product being used while producing the products of higher purity and, lower reflux ratios being used on those fractions which are to be produced at a higher rate for thesake of greater capacity. Thus,there are periods during the distillation of the charge stock lwhen relatively little reilux is returned to column 3 from accumulator. I5, the amount of reilux required depending upon. the quality and purity of the liquid returning to column 3 from hold-up drum 21. In some cases, e. g., when a distillate fraction of relativelyT narrow boiling range produced under relatively high reflux ratio is followed by a distillate fraction of substantially higher boiling range, itwili be found thatthe liquid contained in line 23 is of approximately the desired boiling range and that valve I9 controlling the flow of reflux iniline Iilcan be completely closed, withoutincluding undesirable amounts of higher boiling fractions or components in the distillate.

The rate of return of liquid from hold-up drum 21 through line 28 to column 3 is related tothe rate at which vaporization occurs-and to the rate at which liquid passes downthe tower to drawoif pipe 4S; and the rate of withdrawal of liquid from column 3 through valve 5 and line 25 to hold-up drum 21 is related to the rate at which liquid is allowed toflow from the draw-oil point 4I) down the plates. of the tower below the drawoi point to the still. The-amount of liquid heldup in drum 21 is related to the rates of withdrawal and return to columna and these rates are related line 22, a corresponding decrease in the amount of liquid held-up in drum 21 is experienced. During periods in the distillation when the rate of withdrawal of distillate through line 22 is substantially less than average for the entire distillation, and considerably less than the rate of vaporization from the still, the quantity of liquid held-up in drum 21 will normally be increased at the expense of the liquid remaining in still I.

By alternately conserving and expending the liquid in drum 21 accordingly, as more or less reux is used, a supply of liquid is maintained for return to column 3 near the top so as to augment the supply either of reflux or of distillate, dependtion being distilled is to be relatively narrower or wider.

Consequently, my process provides means for producing, in larger quantities per unit of time than has heretofore been possible, well-fractionated products; and, in still larger quantities, sulcientlyY well-fractionated products .for purposes where a very high degree of purity is not required; and consequently, the process has good flexibility.

In the modification which I have shown in Figure 2, it will be obvious from inspection of the drawings that the essential difference between this modification and my prior described modification resides in the inclusion of a steam stripping tower 32, provision for cooling the steam stripped liquid in cooling coil 36, and the use of a horizontal hold-up drum 21-A containing weirs or perforated partitions 30 which are disposed in said hold-up drum to form a series of compartments 3l in cascade arrangement, so as to reduce the degree of normal free mixing of the various fractions retained in the several compartments 3I. there shown. While I have described hold-up drum 21-A as an-entity with said compartments, in. some instances, such as in the embodiment which will be hereinafter described in conjunction with Figure 4, the said compartments may be separate tanks to which the hold-up liquid is delivered from column 3 according to a progressive cycle; conversely the hold-up liquid may be withdrawn from the Separate compartments of. tanks in the same manner in which the respective fractions were produced. For example, the liquid fraction having the lowest boiling point is pumped back to column 3, while the liquid fractions ci higher boiling range are being accumulated. Flexibility of operation and segregation of fractions of intermediate boiling range may thuswise be obtained. Steam is injected into stripper 32 kthrough line 34 to remove the more volatile fractions from the liquid introduced therein through line 25; steam stripping of the withdrawn liquid contributes to an improved degree of fractionation. The vapors removed from steam stripper 32 arereturned to column 3 by means of line 33. The steam stripped'liquid withdrawn from tower 3 is introduced through line 35 into hold-up drum 21-A which is provided with a series oi' partitions 30 dividing said hold-up drum in cascade into a number of compartments 3 I. Equalizing line 42 connects hold-up drum 21-A and steam stripper 32. In some particular instances, it may be desirable to cool the steam stripped liquid prior to introducing same into hold-up drum ZI-A, and therefore, I have provided cooling coil 33 whereby said liquid may be cooled. In some special instances, it may be preferable and desirable to cool the liquid withdrawn from column 3 after rather than before segregating same in hold-up drum 21-A. When operating with cooling of the steam stripped oil, valve 31 .5 'in line 35 is closed off and valve 39 in line 38 and valve in line 1| are opened thus allowing the oil to pass through cooling coil 36 and thence into hold-up drum' 21-A. As hereinbefore described with relation to Figure 1, the liquid heldup in drum 21-A is pumped to tower 3 by means of pump 29 through line 28. f After the distillation has proceeded and only heavy residue remains in still I, a substantial amount of liquid may be segregated in drum 21-A for removal as a product through'line 44. I have, therefore, provided a means for withdrawing this liquid from hold-up drum 21-A; when desired, valve 45 in line 28 is closed off and valve 43 in line 44 is opened. Thuswise, hold-up drum 21--A may be pumpedlfree of any" liquid remaining therein.

In another preferred modification of my nvention in which batch distillation is conducted in a series of finite steps, reference will now be made to Figure 4 Vin which suitable apparatus elements illustrating the same are shown. A crude petroleum oil is introduced into column 3 from feed tank 56 through line 51 and pump 58. Provision is made whereby the oil contained in tank 56 may be introduced directly into column 3 as described; but when more convenient to do so, the oil from feed tank 56 may be introduced into tank or tanks 59 wherein it mixes with a bottoms fraction withdrawn from column 3 as will be described hereinafter. During the course of the distillation, liquid residue is collected in the bottom of column 3 for reboiling and for withdrawal from column 3. This liquid is withdrawn from column 3 by means of line 60 and a portion of same is pumped by pump 6| through a heating coil 62 disposed in furnace B3 and is returned throughl line 64 to the bottom of the tower at a point above the point of withdrawal but below the bottom plate. A second portion of the oil withdrawn from the bottom of column 3 is cooled in cooler 65 and is thenintroduced through line B6 into tank 59. Alternatively, the bottoms may be heatexchanged against the feed, or stored hot, where heat conservation is a controlling factor. Both feed and liquid residue may be held in the same tank, but it is preferred on principle to Aavoid mixing by the use of more than one tank.

Tanks 59 are alternately filled with liquid residue and emptied by means of pump 61 and feed line 68into column 3 at an intermediate point therein so that some stripping of the oil of its more vola'- tile fractions is thereby effected.l By-pass line l69 is provided so that the charge oil from feed tank 56 may be introduced directly into column 3 at the start of the run while lightest fractions are being distilled. In the modifications which I have described with reference to Figures 1 and 2, the oil is vaporized and passes up the tower, the overhead vapors being withdrawn through line 5 and cooled and condensed in cooling coil I9 and thence accumulated in accumulator I5. The method of withdrawing product and providing reflux to the top of the tower is substantially the same as has been described in connection with Figure 1 and therefore need not be described further herein. In the lower part of column 3, as mentioned before, Ihave provided a draw-off pipe 49 whereby liquid is withdrawn through line 25 to steam stripper 32 wherein more volatile fractions are removed from the withdrawn liquid. The vapors from steam stripper 32 are then introduced into column 3 through line 33. The steam stripped oil is withdrawn from stripper 32 through lines 35 and 38 and is cooled in cooler 36 and is then introduced into the iirst of a series of tanks 3|.?*Provision is made wherebycoolingcoil 36 may be by-passed and the hot strippedv oil delivered directly to tanks 3|. When the oilisvnot cooled, valves 39 and 18 in-lines 38 and 1| are closed and :valve 31 in line 35v is opened, thereby allowing the `stripped 'oil toA be 'delivered 'directly throughline 35 to tanks ,3|.` In a batchidistillation 'conducted ina seriesof'nite steps "as described inthis embodiment, the ilrstv of `the batteryl 'ofi tanks 3 Ifis lled With oil from steam'strip= per.32; and this oil iilling the ilrst of thev aforementioned tanks is of lower boiling point :than the oil which is later introduced into the remaining tanks. It may be readily seen from this description and by reference to Figure 4 that when the viirst of tanks 3| is lled, said tank mayfbe cutout by manipulation of valve 46 in line 41 and the second of the series of tanks may be lled by opening valve 48 in line 49. Successively, the remaining number of tanks may be -lled with successive fractions of progressively higher boiln ing range. Ina like manner the oil in the rst filled tank 3| may be pumped back to tower 3 after opening valve 5| in line 28. And when the saidioil in rst tank 3| has been pumped out through pump 29, in turn, the oil in the second lled tank 3| may be pumped out by opening of valve 52 in line 53 land its contentsret'urned in a like' manner to Vcolumn 3. Likewise the third tank 3| may be emptied by opening valve54 in line 55 and pumping the oil back to the tower 3. Provision'is made for pumping the contents of tanks 3| from the system through valve 43 vand line 44 at the end of the run, the liquid pumped away then comprising distilled fractions of a higher boiling range thanthe products remove through valvel 2|V and line 22..

InY the preferred embodiment which I have described withv relation to Figure 4, a number of advantages are obtained which heretofore `have notbeen possible with batch distillation .equip- 'mentsL Large batches of feed stock can be distilled economically and expeditiously in relatively process with-this particularembodiment -lies in theV recirculation of the'bottoms so thatthe oil is maintained in the heating unit for only a relativeiyshort time, whereby thermal decomposition of the oil, and the expense of large storage `vessels for hot oil, are largely eliminated. Separation of thehoId-uptanks into a series of separate and distinct units provides for greater ,iiexibiliti' irnproved fractionation, andmeans for segregation of fractions of intermediate'boiling range.

In the modifications which I have shown in Figures 1 and 2, and 4, I prefer -to position the draw-off line in such a manner that 25 per cent of the plates of the tower are below line 25, 50 per cent of the plates are between the said line and line 28, and, of course, the remainder of the plates are above line 28. Obviously, there will be situations in which this positioning of lines 25 and 28 may vary within rather wide limits, depending on the stock to be distilled.

It is pointed out that I prefer to proportion the F17 of crudef-petroleum'oriits fractions. 'ForeXam'iple, the-method which I have disclosed may be employed to distill vand purify other` organicliquids ,besides petroleum "fractions, such as alco.- hols,ethers, ketones, esters and the likeri 1 .Particularly useful adaptations of my invention .reside in thesegregation and purincation of (#11) solventfnaphtha-fractions, and (2)high octane number aviation gasoline blending agents, either from natural or syntheticsources, suchy as isopentane, isoheptane, isohexanes, riso-'octan'es andthe like. Other petroleum'or coal tar frac'- tionsfvsuch as'those of the aromatic-type may also-be segregatedand purified by the proce'ssof myinvention. vr fr i To recapitulate, my lpresent; invention relates to 'improvements-in batch distillation of liquids containing a plurality of components. In its essence,"my"invention modies prior practiceby withdrawing from a lower point in a fractionation towerduring distillation'a'quantity of liquid and returning it to amore elevated point in the fractionation column. In this mannerl it is possible to employ less reflux to the top` of the tower than has heretofore been possible and, yet, obtain at an increased rate, well-fractionated products. In

some instances no reflux is required, after the initial phase ofthe distillation. L It isl to be reiterated that 'the invention resides in theprovision of a yhot material withdrawn at an `intermediate Apoint from the fractionation tower andthe return of same toia point higher up in the tower than the point ci withdrawal. Thetype ofpacking employed vin theA fractionation =tower is not'i critical. For example, the tower maybe of the bubble cap type with trays or it may be packedwith Raschig rings', screen packing, or with any equivalent means whereby intimate contact between vapors and liquids is attained.

Itis also to be understood that while I-,have described my invention with respect" to providing reux in the top of the tower by pumping a por- Vtionof the product back-to column 3' above the top plate thereof, thismethod i's'for illustrative vpurposes only, since other means'iorinducing reflux in the top of tower may be employed such as by use of partial condensers or other equivalent means." i. Many modications otY my inventionl will readily suggest themselves to thos'efarniliar with this particular art.

`I claim: l. In the batch distillation of liquids containing a'plurality'jof components, `the improvement which comprises heating said liquid to form vapors,discharging said vapors into the bottom of a4 vertical fractionating tower; successively withdrawing a pluralitvoi liquidomponents ofdifferent boiling ranges -from afpoint in the lower part of said-tower Vas the distillation proceeds, maintaining said 4withdrawn' components-separately and segregated in an accumulation zone andreturning the segregated components to the tower in the order of their withdrawal therefrom at a point ini the tower more `elevated than their point oiwithdrawal and separated froniithe lat- `ter -by interior -fractionating structurewhereby the amountrof reflux normally employed and recycled to the top of; the'tower is-substantially reduced.

2. In the batch distillation Aof liquids containing a plurality ofA components, the improvement which comprises heating said liquid to form vapors, dischargingsaid vapors into the bottom of a vertical fractionating tower, successively withdrawing a plurality of liquid components of diierent boiling ranges from. a point in the lower part' of'said tower as the distillation proceeds, cooling ythe withdrawn components, maintaining saidwithdrawn components'separately and segregated inran accumulation zone and returning the segregated components to the tower in the order of their withdrawal therefrom-.at a point inthe tower more elevated than their point of withdrawal andl separated from the latter by i11- terio'r ,f fractionating structure whereby the amount of reiux normally employed and recycled tothe top-of the tower is' substantially re- 3. In the batch distillation of liquids' containing a plurality -of components, the improvement which comprises heating said liquid to form vapors, discharging said vapors into thebottom of a vertical fractionating tower, withdrawing a plurality of liquid components of diierent boiling ranges from-a point in the lower part of said tower; discharging said withdrawn liquid components into an accumulation Zone and returning the liquid components tothe tower at a point inthe tower where the boilingrange 'of the liq-i uid inthe tower corresponds substantially to the boilingrange of the liquid being returned thereto'whereby the amount of reflux normally employed and recycled to the top ofv thel tower is substantially'reduced. A 'GEORGE 'I'. A'IKINS, JR'. 

